CN106243318B - A kind of mixing calendering type thermoplastic polyurethane elastomer and preparation method thereof - Google Patents
A kind of mixing calendering type thermoplastic polyurethane elastomer and preparation method thereof Download PDFInfo
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- CN106243318B CN106243318B CN201610613195.6A CN201610613195A CN106243318B CN 106243318 B CN106243318 B CN 106243318B CN 201610613195 A CN201610613195 A CN 201610613195A CN 106243318 B CN106243318 B CN 106243318B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6212—Polymers of alkenylalcohols; Acetals thereof; Oxyalkylation products thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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Abstract
The present invention provides a kind of mixing calendering type thermoplastic polyurethane elastomer and preparation method thereof, the thermoplastic polyurethane elastomer is prepared by 20-35 parts by weight diisocyanate, 40-60 weight polyol, 10-25 weight account polyethylene alcohol resin, 15-30 weight part polycarbonate, 1-8 parts by weight chain extender and 1-3 part by weight of catalyst, wherein the polyalcohol is the mixture of the pure and mild polyester polyol of polyether polyols.It is cooperated by each component, so that polyurethane elastomer has favorable elasticity and processability, anti-adhesion performance improves, and polyvinyl alcohol resin and polycarbonate have synergistic effect in the performance for further increase polyurethane elastomer, and the tensile strength of gained polyurethane elastomer reaches 85MPa or more, elongation at break is up to 950%, rebound degree reaches 85% or more, and adhesive force is 0 grade, does not stick together, roll suitable for mixing, will not be adhered to metal device in mixing calender line.
Description
Technical field
The invention belongs to polymeric material field, it is related to a kind of mixing calendering type thermoplastic polyurethane elastomer and its preparation
Method.
Background technique
Thermoplastic polyurethane (TPU) is a kind of novel organic polymer synthetic material, and properties are excellent, Ke Yidai
For rubber, soft polyvinyl chloride material PVC.Such as it with excellent physical property, such as wearability, screen resilience is all better than general
Logical polyurethane and PVC, resistance to ag(e)ing be better than rubber, it may be said that are the optimal materials of substitution PVC and PU.
CN103289360A discloses a kind of calenderability thermoplastic polyurethane and preparation method thereof, but its way is will to add
Agent (whale rouge cured and hard soap) outside double-screw reactor posterior segment in making an addition in TPU melt.This method is due to adding
Adding agent is powder state, and the stability of outer addition manner is insufficient, can not be dispersed in TPU melt, and it is used to roll
Product surface afterwards will appear serious auxiliary agent precipitation phenomenon.
Therefore, in the art, it is expected that developing a kind of polyurethane elastomer suitable for mixing calendering.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of mixing calendering type thermoplastic polyurethane elastics
Body and preparation method thereof.Thermoplastic polyurethane elastomer of the invention has good elasticity, and good processing performance is suitable for
Mixing calendering, the product for not adhering to, and being prepared with metal equipment in mixing calender line are not easy xanthochromia, and heat resistance is good
It is good.
To achieve this purpose, the present invention adopts the following technical scheme:
On the one hand, the present invention provides a kind of mixing calendering type thermoplastic polyurethane elastomer, the thermoplastic polyurethane bullet
Property body is mainly prepared by following raw material:
Wherein the polyalcohol is the mixture of the pure and mild polyester polyol of polyether polyols.
In the present invention, diisocyanate and polyalcohol are selected in amount ranges described above, under the dosage, hard section
Cooperated well with soft segment, polyvinyl alcohol resin and polycarbonate is cooperated further to adjust polyurethane on basis herein
Elasticity, and enhance its malleability energy, polyurethane elastomer made to have good bullet under the mutual cooperation of each component
Property and processability, and polyvinyl alcohol resin and polycarbonate have in the performance for further increase polyurethane elastomer
Synergistic effect.
In the present invention, the dosage of the diisocyanate can be 21 parts by weight, 23 parts by weight, 25 parts by weight, 27 weights
Measure part, 29 parts by weight, 30 parts by weight, 32 parts by weight or 34 parts by weight.
In the present invention, the dosage of the polyether polyol can be 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 weights
Measure part, 50 parts by weight, 52 parts by weight, 55 parts by weight or 58 parts by weight.
In the present invention, the dosage of the polyvinyl alcohol resin can be 12 parts by weight, 14 parts by weight, 16 parts by weight, 18
Parts by weight, 20 parts by weight, 22 parts by weight or 24 parts by weight.
In the present invention, the dosage of the polycarbonate can be 16 parts by weight, 18 parts by weight, 20 parts by weight, 22 weight
Part, 24 parts by weight, 26 parts by weight or 28 parts by weight.
In the present invention, the dosage of the chain extender can be 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 weights
Measure part or 7 parts by weight.
In the present invention, the dosage of the catalyst can be 1.3 parts by weight, 1.5 parts by weight, 1.8 parts by weight, 2 weight
Part, 2.2 parts by weight, 2.4 parts by weight, 2.6 parts by weight or 2.8 parts by weight.
Preferably, the thermoplastic polyurethane elastomer is mainly prepared by following raw material:
It is further preferred that the thermoplastic polyurethane elastomer is mainly prepared by following raw material:
In the present invention, the diisocyanate be toluene di-isocyanate(TDI), it is hydrogenated diphenyl methane diisocyanate, different
One of isophorone diisocyanate or methyl diphenylene diisocyanate or at least two combination, preferred isophorone two
Isocyanates.
Preferably, the mass ratio of the pure and mild polyester polyol of polyether polyols is 1:(2-4 in the polyalcohol), such as 1:2,1:
2.3,1:2.5,1:2.8,1:3,1:3.2,1:3.5,1:3.8 or 1:4, preferably 1:3.In the present invention, by will be in polyalcohol
The mass ratio of the pure and mild polyester polyol of polyether polyols is controlled in 1:(2-4), it can preferably adjust matching between hard section and soft segment
Than so that elasticity is just, processing performance is more preferable.
Preferably, the number-average molecular weight of the polyalcohol be 4000-6000, such as 4000,4200,4400,4600,
4800,5000,5300,5500,5800 or 6000.
Preferably, the chain extender is any one in ethylene glycol, 1,3-PD, 1,4-butanediol or 1,5-PD
Kind or at least two combination.
Preferably, the catalyst be in stannous octoate, two sad two fourth tin or two fourth tin of moon silicic acid any one or
At least two combination.
On the other hand, the present invention provides mixing calendering type method for preparing thermoplastic polyurethane elastomer as described above,
It the described method comprises the following steps:
(1) diisocyanate, polyether polyol, chain extender, catalyst are added to the container, under agitation, vacuum
Dehydration, then 110-130 DEG C (such as 113 DEG C, 115 DEG C, 118 DEG C, 120 DEG C, 125 DEG C or 128 DEG C) reaction 2-5h (such as
2.3h, 2.5h, 3h, 3.5h, 4h, 4.5h or 4.8h)；
(2) polyvinyl alcohol resin and polycarbonate are added into the reaction mass of step (1), after mixing, using double
Screw extruder extruding pelletization obtains the mixing calendering type thermoplastic polyurethane elastomer.
Preferably, temperature when step (1) described vacuum dehydration be 60-80 DEG C, such as 60 DEG C, 63 DEG C, 65 DEG C, 68 DEG C,
70 DEG C, 73 DEG C, 75 DEG C, 78 DEG C or 80 DEG C.
Preferably, the rate of step (1) described stirring be 1000-1500r/min, such as 1000r/min, 1100r/min,
1200r/min, 1300r/min, 1400r/min or 1500r/min.
Preferably, pressure when step (1) described vacuum dehydration be -0.3~-0.1kPa, such as -0.3kPa, -
0.28kPa, -0.25kPa, -0.23kPa, -0.2kPa, -0.18kPa, -0.15kPa, -0.13kPa or -0.1kPa.
Preferably, the feeding section temperature of step (2) described double screw extruder is 120-130 DEG C, such as 122 DEG C, 125
DEG C, 128 DEG C or 130 DEG C, mixing section temperature is 140-150 DEG C, such as 142 DEG C, 144 DEG C, 146 DEG C, 148 DEG C or 150 DEG C, is squeezed out
Duan Wendu is 160-180 DEG C, such as 162 DEG C, 165 DEG C, 168 DEG C, 170 DEG C, 173 DEG C, 175 DEG C or 178 DEG C, head temperature is
170-180 DEG C, such as 170 DEG C, 173 DEG C, 175 DEG C or 178 DEG C.
As optimal technical scheme, mixing calendering type method for preparing thermoplastic polyurethane elastomer tool of the present invention
Body the following steps are included:
(1) diisocyanate, polyether polyol, chain extender, catalyst are added to the container, are turned in 1000-1500r/min
Under speed stirring, it is dehydrated in -0.3~-0.1kPa vacuum under pressure, then in 110-130 DEG C of reaction 2-5h；
(2) polyvinyl alcohol resin is added into the reaction mass of step (1), after mixing, utilizes double screw extruder
Extruding pelletization, the feeding section temperature of the double screw extruder are 120-130 DEG C, and mixing section temperature is 140-150 DEG C, extruding zone
Temperature is 160-180 DEG C, and head temperature is 170-180 DEG C, obtains the mixing calendering type thermoplastic polyurethane after extruding pelletization
Elastomer.
Compared with the existing technology, the invention has the following advantages:
The present invention is cooperated using diisocyanate and polyalcohol, is adjusted between soft segment and hard section by adjusting its dosage
Proportionate relationship, and cooperate polyvinyl alcohol resin and polycarbonate, each component cooperates so that polyurethane elastomer have it is good
Good elasticity and processability, anti-adhesion performance improves, and polyvinyl alcohol resin and polycarbonate are further increasing poly- ammonia
There is synergistic effect in the performance of ester elastomer.After measured, the tensile strength of gained polyurethane elastomer reaches 85MPa or more,
Elongation at break reaches 950%, and rebound degree reaches 85% or more, and adhesive force is 0 grade, and 8h is placed at 80 DEG C and is not sticked together,
Roll suitable for mixing, will not be adhered to metal device in mixing calender line.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
In the present embodiment, thermoplastic polyurethane elastomer is mainly prepared by following raw material:
Wherein the polyalcohol is the mixture of the pure and mild polyester polyol of polyether polyols, the pure and mild polyester polyol of polyether polyols
Mass ratio be 1:3, the number-average molecular weight of polyalcohol is 6000, and the diisocyanate is isophorone diisocyanate, institute
Stating chain extender is 1,3-PD, and the catalyst is stannous octoate.
The preparation method is as follows:
(1) diisocyanate, polyether polyol, chain extender, catalyst are added to the container, are stirred in 1200r/min revolving speed
It mixes down, is dehydrated in -0.1kPa vacuum under pressure, then in 120 DEG C of reaction 3h；
(2) polyvinyl alcohol resin is added into the reaction mass of step (1), after mixing, utilizes double screw extruder
Extruding pelletization, the feeding section temperature of the double screw extruder are 120 DEG C, and mixing section temperature is 140 DEG C, and extruding zone temperature is
160 DEG C, head temperature is 180 DEG C, and the mixing calendering type thermoplastic polyurethane elastomer is obtained after extruding pelletization.
Embodiment 2
In the present embodiment, thermoplastic polyurethane elastomer is mainly prepared by following raw material:
Wherein the polyalcohol is the mixture of the pure and mild polyester polyol of polyether polyols, the pure and mild polyester polyol of polyether polyols
Mass ratio be 1:2, the number-average molecular weight of polyalcohol is 5000, and the diisocyanate is isophorone diisocyanate, institute
Stating chain extender is 1,3-PD, and the catalyst is stannous octoate.
The preparation method is as follows:
(1) diisocyanate, polyether polyol, chain extender, catalyst are added to the container, are stirred in 1500r/min revolving speed
It mixes down, is dehydrated in -0.3kPa vacuum under pressure, then in 130 DEG C of reaction 2h；
(2) polyvinyl alcohol resin is added into the reaction mass of step (1), after mixing, utilizes double screw extruder
Extruding pelletization, the feeding section temperature of the double screw extruder are 130 DEG C, and mixing section temperature is 140 DEG C, and extruding zone temperature is
180 DEG C, head temperature is 170 DEG C, and the mixing calendering type thermoplastic polyurethane elastomer is obtained after extruding pelletization.
Embodiment 3
In the present embodiment, thermoplastic polyurethane elastomer is mainly prepared by following raw material:
Wherein the polyalcohol is the mixture of the pure and mild polyester polyol of polyether polyols, the pure and mild polyester polyol of polyether polyols
Mass ratio be 1:4, the number-average molecular weight of polyalcohol is 4000, and the diisocyanate is isophorone diisocyanate, institute
Stating chain extender is 1,3-PD, and the catalyst is stannous octoate.
The preparation method is as follows:
(1) diisocyanate, polyether polyol, chain extender, catalyst are added to the container, are stirred in 1000r/min revolving speed
It mixes down, is dehydrated in -0.2kPa vacuum under pressure, then in 110 DEG C of reaction 5h；
(2) polyvinyl alcohol resin is added into the reaction mass of step (1), after mixing, utilizes double screw extruder
Extruding pelletization, the feeding section temperature of the double screw extruder are 130 DEG C, and mixing section temperature is 150 DEG C, and extruding zone temperature is
160 DEG C, head temperature is 170 DEG C, and the mixing calendering type thermoplastic polyurethane elastomer is obtained after extruding pelletization.
Embodiment 4
In the present embodiment, thermoplastic polyurethane elastomer is mainly prepared by following raw material:
Wherein the polyalcohol is the mixture of the pure and mild polyester polyol of polyether polyols, the pure and mild polyester polyol of polyether polyols
Mass ratio be 1:3, the number-average molecular weight of polyalcohol is 6000, and the diisocyanate is isophorone diisocyanate, institute
Stating chain extender is 1,3-PD, and the catalyst is stannous octoate.
The preparation method is as follows:
(1) diisocyanate, polyether polyol, chain extender, catalyst are added to the container, are stirred in 1200r/min revolving speed
It mixes down, is dehydrated in -0.1kPa vacuum under pressure, then in 120 DEG C of reaction 3h；
(2) polyvinyl alcohol resin is added into the reaction mass of step (1), after mixing, utilizes double screw extruder
Extruding pelletization, the feeding section temperature of the double screw extruder are 120 DEG C, and mixing section temperature is 150 DEG C, and extruding zone temperature is
160 DEG C, head temperature is 180 DEG C, and the mixing calendering type thermoplastic polyurethane elastomer is obtained after extruding pelletization.
Comparative example 1
The comparative example difference from Example 1 is only that polyalcohol is polyether polyol, in addition to this, remaining raw material
It is same as Example 1 with raw material dosage and preparation method.
Comparative example 2
The comparative example difference from Example 1 is only that polyalcohol is polyester polyol, in addition to this, remaining raw material
It is same as Example 1 with raw material dosage and preparation method.
Comparative example 3
The comparative example difference from Example 1 is only that, the quality of the pure and mild polyester polyol of polyether polyols in polyalcohol
Than for 1:1, in addition to this, remaining raw material and raw material dosage and preparation method are same as Example 1.
Comparative example 4
The comparative example difference from Example 1 is only that, the quality of the pure and mild polyester polyol of polyether polyols in polyalcohol
Than for 1:5, in addition to this, remaining raw material and raw material dosage and preparation method are same as Example 1.
Comparative example 5
The comparative example difference from Example 1 is only that the number-average molecular weight of polyalcohol is 7000, in addition to this,
Remaining raw material and raw material dosage and preparation method are same as Example 1.
Comparative example 6
The comparative example difference from Example 1 is only that the number-average molecular weight of polyalcohol is 3500, in addition to this,
Remaining raw material and raw material dosage and preparation method are same as Example 1.
Comparative example 7
The comparative example difference from Example 1 is only that, does not include polyvinyl alcohol tree in the raw material of polyurethane elastomer
Rouge, in addition to this, remaining raw material and raw material dosage and preparation method are same as Example 1.
Comparative example 8
The comparative example difference from Example 1 is only that, does not include polyvinyl alcohol tree in the raw material of polyurethane elastomer
Rouge, the dosage of polycarbonate are 37 parts by weight, and in addition to this, remaining raw material and raw material dosage and preparation method are and embodiment
1 is identical.
Comparative example 9
The comparative example difference from Example 1 is only that, is not included polycarbonate in the raw material of polyurethane elastomer, is removed
Except this, remaining raw material and raw material dosage and preparation method are same as Example 1.
Comparative example 10
The comparative example difference from Example 1 is only that, does not include polycarbonate in the raw material of polyurethane elastomer, is gathered
The dosage of vinyl alcohol resin is 37 parts by weight, in addition to this, remaining raw material and raw material dosage and preparation method with embodiment 1
It is identical.
Embodiment 1-4 and comparative example the 1-11 polyurethane elastomer being prepared are tested for the property, as a result such as table 1
It is shown.
Table 1
The present invention uses the diisocyanate and polyalcohol of specific consumption proportion it can be seen from the result of table 1, and matches
Polyvinyl alcohol resin is closed, each component is under specific consumption proportion, and interaction is mutually coordinated, so that the polyurethane being prepared
With good mechanical performance and processability, elasticity is good, and anti-adhesion performance improves.After measured, gained polyurethane elastomer
Tensile strength reaches 85MPa or more, and elongation at break reaches 950%, and rebound degree reaches 85% or more, and adhesive force is 0 grade, 80
8h is placed at DEG C not stick together, and is suitable for calendering, will not be adhered to metal device in calender line.
The Applicant declares that the present invention is explained by the above embodiments polyurethane elastomer and its preparation side of the invention
Method, but the present invention is not limited to the above embodiments, that is, does not mean that the present invention must rely on above-described embodiment and could implement.Institute
Belong to those skilled in the art it will be clearly understood that any improvement in the present invention, to the equivalence replacement of each raw material of product of the present invention
And addition, selection of concrete mode of auxiliary element etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (14)
1. a kind of mixing calendering type thermoplastic polyurethane elastomer, which is characterized in that the thermoplastic polyurethane elastomer by with
Lower raw material is prepared:
Diisocyanate 20-35 parts by weight
Polyalcohol 40-60 parts by weight
Polyvinyl alcohol resin 10-25 parts by weight
Polycarbonate 15-30 parts by weight
Chain extender 1-8 parts by weight
Catalyst 1-3 parts by weight；
Wherein the polyalcohol is the mixture of the pure and mild polyester polyol of polyether polyols；
The mass ratio of the pure and mild polyester polyol of polyether polyols is 1:(2-4 in the polyalcohol)；
The number-average molecular weight of the polyalcohol is 4000-6000.
2. mixing calendering type thermoplastic polyurethane elastomer according to claim 1, which is characterized in that the thermoplastic poly
Urethane elastomer is prepared by following raw material:
Diisocyanate 25-30 parts by weight
Polyalcohol 45-55 parts by weight
Polyvinyl alcohol resin 15-20 parts by weight
Polycarbonate 20-25 parts by weight
Chain extender 2-4 parts by weight
Catalyst 1-2 parts by weight.
3. mixing calendering type thermoplastic polyurethane elastomer according to claim 2, which is characterized in that the thermoplastic poly
Urethane elastic body active will be prepared by following raw material:
28 parts by weight of diisocyanate
50 parts by weight of polyalcohol
15 parts by weight of polyvinyl alcohol resin
22 parts by weight of polycarbonate
3 parts by weight of chain extender
1 parts by weight of catalyst.
4. mixing calendering type thermoplastic polyurethane elastomer according to claim 1, which is characterized in that the diisocyanate
Ester is toluene di-isocyanate(TDI), hydrogenated diphenyl methane diisocyanate, isophorone diisocyanate or diphenyl methane two
One of isocyanates or at least two combination.
5. mixing calendering type thermoplastic polyurethane elastomer according to claim 4, which is characterized in that the diisocyanate
Ester is isophorone diisocyanate.
6. mixing calendering type thermoplastic polyurethane elastomer according to claim 1, which is characterized in that in the polyalcohol
The mass ratio of the pure and mild polyester polyol of polyether polyols is 1:3.
7. mixing calendering type thermoplastic polyurethane elastomer according to claim 1, which is characterized in that the chain extender is
In ethylene glycol, 1,3- propylene glycol, 1,4- butanediol or 1,5- pentanediol any one or at least two combination.
8. mixing calendering type thermoplastic polyurethane elastomer according to claim 1, which is characterized in that the catalyst is
In stannous octoate, two sad two fourth tin or two fourth tin of moon silicic acid any one or at least two combination.
9. mixing calendering type method for preparing thermoplastic polyurethane elastomer according to claim 1 to 8,
It is characterized in that, the described method comprises the following steps:
(1) diisocyanate, polyether polyol, chain extender, catalyst are added to the container, under agitation, vacuum dehydration,
Then in 110-130 DEG C of reaction 2-5h；
(2) polyvinyl alcohol resin is added into the reaction mass of step (1) and polycarbonate utilizes twin-screw after mixing
Extruder extruding pelletization obtains the mixing calendering type thermoplastic polyurethane elastomer.
10. preparation method according to claim 9, which is characterized in that temperature when step (1) described vacuum dehydration is
60-80℃。
11. preparation method according to claim 9, which is characterized in that the rate of step (1) described stirring is 1000-
1500 r/min。
12. preparation method according to claim 9, which is characterized in that pressure when step (1) described vacuum dehydration is-
0.3~-0.1kPa.
13. preparation method according to claim 9, which is characterized in that the feeding section of step (2) described double screw extruder
Temperature is 120-130 DEG C, and mixing section temperature is 140-150 DEG C, and extruding zone temperature is 160-180 DEG C, head temperature 170-180
℃。
14. preparation method according to claim 9, which is characterized in that the described method comprises the following steps:
(1) diisocyanate, polyether polyol, chain extender, catalyst are added to the container, in 1000-1500 r/min revolving speed
Under stirring, it is dehydrated in -0.3~-0.1kPa vacuum under pressure, then in 110-130 DEG C of reaction 2-5h；
(2) polyvinyl alcohol resin is added into the reaction mass of step (1), after mixing, is squeezed out using double screw extruder
It is granulated, the feeding section temperature of the double screw extruder is 120-130 DEG C, and mixing section temperature is 140-150 DEG C, extruding zone temperature
It is 160-180 DEG C, head temperature is 170-180 DEG C, obtains the mixing calendering type thermoplastic polyurethane elastic after extruding pelletization
Body.
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